Ionic compound and olefin polymerization catalyst containing the same

ABSTRACT

Ionic compounds represented by general formula (I), method of their production, olefin polymerization catalyst components, and olefin polymerization catalysts containing the components are provided. 
     
          M(R.sup.1).sub.k (R.sup.2).sub.1 (R.sup.3).sub.m (R.sup.4 -L).sub.n 
    
      ! -   D! +                                          (I) 
     (wherein, M is an element belonging to the Group 13; R 1 , R 2  and R 3  are pentafluorophenyl, etc., R 4  is a substituted phenylene group, etc., k, l and m being each 0 or an integer of 1 to 3, and n being an integer of 1 to 4 such that k+l+m+n=4; L is trichlorosilyl, methyldichlorosilyl, dimethylchlorosilyl group, etc.; and D is a monovalent cation). The catalyst of this invention, which is used in combination with the ionic compound of this invention, a carrier, an organometal compound and a Group 4, 5 or 6 transition metal compound, has high activity so that polymerization of olefins by a slurry process, a gas phase process or the like using the catalyst gives rise to a polymer having good powder characteristics and attachment of the polymer to the reactor is minimized.

This application is a 371 of PCT/JP96/01514 filed Jun. 5, 1996.

FIELD OF THE INVENTION

This invention relates to ionic compounds, method for preparing thesame, olefin polymerization catalyst components containing the same, andolefin polymerization catalyst compositions containing the components.

BACKGROUND OF THE INVENTION

Heretofore, there has been known a method of producing olefins using ametallocene compound and methylaluminoxane as a catalyst in ahomogeneous system. For example, Japanese Patent Application Laid-openNo. 19309/1983 discloses a method of producing ethylene homopolymers andethylene/C₃ -C₁₂ α-olefin copolymers using biscyclopentadienyl zirconiumdichloride and a linear or cyclic methylaluminoxane as a catalyst.Japanese Patent Application Laid-open No. 130314/1986 discloses a methodof producing stereoregular polypropylenes using a catalyst comprising azirconium compound containing as a ligand a compound having two indenylgroups intervened with an ethylene group and aluminoxane. Also, JapanesePatent Application Laid-open No. 41303/1990 discloses a method ofproducing poly-α-olefins having a good syndiotacticity.

There have also been proposed catalyst composition systems that use noaluminoxane cocatalyst. Taube et al. performed polymerization ofethylene using a metallocene represented by Cp₂ TiMe(THF)!⁻ BPh₄ !⁺ (Cp:a cyclopentadienyl group, Me: a methyl group, THF: a tetrahydrofuranylgroup, Ph: a phenyl group) (J. Organometall. Chem., 347, C9 (1988)). InJ. Am. Chem. Soc., 109, 4111 (1987), Jordan et al. reported that azirconium complex represented by Cp₂ ZrR(L)!⁻ (Cp: a cyclopentadienylgroup, R: a methyl group or a benzyl group, L: a Lewis base) functionsas a catalyst for polymerization of ethylene. Japanese PatentApplication Laid-open Nos. 501950/1989 and 502036/1989 disclose methodsof polymerizing olefins using catalysts comprising a cyclopentadienylmetal compound and an ionic compound which can stabilize thecyclopentadienyl metal cations. Zambelli et al. reported that use of acatalyst which comprises a zirconium compound having a cyclopentadienederivative as a ligand, trimethylaluminum and fluorodimethylaluminumenables production of isotactic polypropylenes (macromolecules, 22, 2186(1989)).

However, use of the above-described catalysts, when used in slurrysystem processes or gaseous system processes, caused problems since thepolymer is produced in the form of fine powder having a low bulk densityand, hence, it is difficult to handle it and the polymer producedattaches to an inner wall of the reactor.

In order to solve these problems, various proposals have been made tohave the catalysts carried on solid carriers.

For example, Japanese Patent Application Laid-open Nos. 108610/1986,296008/1986, 280703/1988, 22804/1988, 51405/1988, 51407/1988,55403/1988, 61010/1988, 248803/1988, 100808/1992, 74412/1991, 709/1991and 7306/1992 disclose methods of producing olefins using solidcatalysts comprising inorganic metal oxides such as silica, alumina,silica-alumina and the like having carried thereon metallocene compoundsand methylaluminoxane, respectively.

Japanese Patent Application Laid-open Nos. 6003/1989, 6004/1989,6005/1989, 11104/1989 and 11105/1989 disclose methods in which catalystsare used that comprise a metallocene compound and aluminoxane carried onan organometallic magnesium compound.

Also, Japanese Patent Application Laid-open Nos. 260903/1988, 31403/1992and 74411/1991 disclose polymerization methods in which catalysts areused that comprise a metallocene compound and aluminoxane carried onpolymer such as polyethylene, polystyrene, respectively.

Japanese Patent Application Laid-open Nos. 276805/1986 and 74415/1991disclose polymerization methods using a metal oxide and a metallocenecompound having carried thereon only methylaluminoxane.

Further, Japanese Patent Application Laid-open Nos. 259004/1989,259005/1989, 56928/1994 and 56929/1994 disclose methods in whichcatalysts are used that comprise a metallocene compound having a specialligand, carried on a porous metal oxide carrier, such as silica. On theother hand, Japanese Patent Application Laid-open No. 234405/1992discloses a method of solidifying a catalyst using a cyclopentadienylgroup bonded to a poly(halogenated methylstyrene) to form a complex withthe catalyst.

Studies have been made in order to obtain solidified catalysts forcatalyst systems using no aluminoxane cocatalyst. For example, JapanesePatent Application Laid-open No. 234709/1991, 247128/1993, 239138/1993,148316/1993, 155926/1993 and 502906/1993 disclose methods in whichcatalysts are used that comprise a cation type metallocene compoundreacted with a non-coordinating boron compound carried on an inorganicmetal compound such as silica. However, in these carrying methods, theboron compound is not bonded to the carrier so that upon polymerization,activated species come off from the surface of the carrier, causing theresulting resin to attach to the reactor.

Further, Japanese Patent Application Laid-open No. 501573/1995 (WO93/11172) discloses a method involving use of an ion-activated transientmetal catalyst composition useful for the polymerization of olefins, thecomposition comprising a core portion and a polyanionic transient metalcatalyst component, i.e., a polyanion portion comprising a plurality ofmetal- or metalloid atom-containing non-coordinating anionic groupchemically bonded to the core portion as a side chain. Here, the coreportion is comprised by (1) an oligomer of a salt of a polymerizableanionic portion containing a metalloid atom and an organic cationprepared in the presence of a metallocene, (2) cross-linked particles ofa polymer such as a styrene based polymer, or (3) inorganic particlessuch as those of glass, silica, metal, etc. In the above-describedpublication, there are described examples which used the former two((1), (2)) as the core and confirmed their effect as a polymerizationcatalyst. However, when the present inventors tested the examples, themethod was insufficient in either one of the activity of olefinpolymerization, powder characteristics of the resulting polyolefins, andattachment of the polymers to the reactor.

Therefore, an object of this invention is to provide a carrier-supportedolefin polymerization catalyst which is excellent in the activity ofcatalyst and has solved the problem involved in the conventional methodsthat the resulting polymer attaches to the wall of the reactor and toprovide an ionic compound for use therein.

SUMMARY OF THE INVENTION

The present inventors have made intensive research in order to solve theabove-described problems and as a result have discovered a Group 13element (after the 1990 Rule for Nomenclature of InorganicCompounds)-containing ionic compound having a functional group which isbondable to a carrier and found that highly active polymer which doesnot attach to the inner wall of the reactor can be obtained byperforming polymerization of olefins using an olefin polymerizationcatalyst comprising a carrier to which the ionic compound is chemicallybonded, an organic metal and a transient metal compound belonging to theGroup IV, V or VI of the periodic table.

That is, this invention provides the ionic compounds, methods ofproducing the same, catalyst components for olefin polymerizationcatalysts, and olefin polymerization catalysts containing the componentsdescribed below.

1) Ionic compounds represented by general formula (I) below:

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -L).sub.n !.sup.-  D!.sup.+                                         (I)

(wherein, M is an element belonging to the Group 13;

R¹, R² and R³, which may be the same or different, represent each a C₁-C₂₀ hydrocarbyl group, a substituted hydrocarbyl group, an alkoxidegroup, or a halogen atom;

R4 represents a C₁ -C₂₀ alkylene group, a substituted alkylene group, asubstituted phenylene group, a silanylene group, a substitutedsilanylene group, a silalkylene group, a substituted silalkylene group,an oxasilanylene group, a substituted oxasilanylene group, or anoxasilalkylene group, with k, l and m being each 0 or an integer of 1 to3, and n being an integer of 1 to 4 such that k+l+m+n=4;

L is a group represented by general formula (II) or (III) below and ischemically bonded to R⁴ :

    SiR.sup.5 R.sup.6 R.sup.7                                  (II)

    R.sup.8 R.sup.9 R.sup.10 SiYSiR.sup.11 R.sup.12            (III)

(wherein R⁵ to R¹², which may be the same or different, represent each aC₁ -C₂₀ hydrocarbyl group, a substituted hydrocarbyl group, an alkoxidegroup, or a halogen atom, with at least one of R⁵, R⁶ and R⁷ and atleast one of R⁸, R⁹ and R¹⁰ being a halogen atom;

Y is --O--, a C₁ -C₂₀ alkylene group, a substituted alkylene group, aphenylene group, a substituted phenylene group, or a group representedby formula:

    --(Z.sup.1 SiZ.sup.2 Z.sup.3 Z.sup.4).sub.r --

(wherein Z¹ and Z⁴, which may be the same or different, represent eachan alkylene group, a substituted alkylene group, a phenylene group, asubstituted phenylene group, --O--, an oxyalkylene group, a substitutedoxyalkylene group, an oxyphenylene group, or a substituted oxyphenylenegroup; Z² and Z³, which may be the same or different, represent each ahydrogen atom, an alkyl group, a substituted alkyl group, a phenylgroup, or a substituted phenyl group; r is an integer of at least 1););

when n is 2 or more, each R⁴ -L may be the same or different;

D is a monovalent cation selected from the group consisting ofcarbonium, anilinium, ammonium, ferrocenium, phosphonium, sodium,potassium, or lithium).

2) The ionic compound described in 1) above, wherein n is 1.

3) The ionic compound described in 1) above, wherein M is boron.

4) The ionic compound described in 1) above, wherein R¹, R² and R³ areeach a pentafluorophenyl group.

5) The ionic compound described in 1) above, wherein L is a halogenatedsilyl group, a halogenated substituted silyl group, a halogenatedsilalkyl group, a halogenated substituted silalkyl group, a halogenatedoxasilyl group, a halogenated substituted oxasilyl group, or ahalogenated oxasilalkyl group.

6) The ionic compound described in 1) above, wherein R⁴ is a substitutedphenylene group.

7) The ionic compound described in 6) above, wherein R⁴ is a2,3,5,6-tetrafluorophenylene group.

8) The ionic compound described in 1) above, wherein L is atrichlorosilyl group, a methyldichlorosilyl group, or adimethylchlorosilyl group.

9) The ionic compound described in 1) above, wherein D is an aniliniumion.

10) A method of producing ionic compounds represented by general formula(I)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -L).sub.n !.sup.-  D!.sup.+                                         (I)

(wherein the symbols in the formula have the same meanings as in 1)above) comprising using components represented by (1) to (4) below:

(1) A compound represented by general formula (IV):

    X.sup.1 -R.sup.4 -X.sup.2                                  (IV)

(wherein X¹ and X² independently represent a hydrogen atom or a bromineatom, and R⁴ has the same meaning as in 1) above);

(2) A compound represented by general formula (V):

    MR.sup.1 R.sup.2 R.sup.3                                   (V)

(wherein M is an element belonging to the Group 13; and R¹, R² and R³,which may be the same or different, represent each a C₁ -C₂₀ hydrocarbylgroup, substituted hydrocarbyl group, or alkoxide group or a halogenatom);

(3) A compound represented by general formula (VI) or (VII):

    SiR.sup.5 R.sup.6 R.sup.7 R.sup.13                         (VI)

    R.sup.8 R.sup.9 R.sup.10 SiYSiR.sup.11 R.sup.12 R.sup.14   (VII)

(wherein R⁵ to R¹⁴ have the same meanings as in 1) above); and

(4) A halide of a monovalent cation.

11) A method of producing ionic compounds represented by general formula(I)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -L).sub.n !.sup.-  D!.sup.+                                         (I)

(wherein the symbols in the formula have the same meanings as in 1)above) comprising the steps of:

(a) substituting bromine or hydrogen at the a compound represented bygeneral formula (IV)

    X.sup.1 -R.sup.4 -X.sup.2                                  (IV)

(wherein the symbols in the formula have the same meanings as in 10)above) by lithium with an organic lithium to obtain a lithiumsubstituted compound;

(b) reacting the lithium substituted compound with a Group 13 elementcontaining compound represented by general formula (V)

    MR.sup.1 R.sup.2 R.sup.3                                   (V)

(wherein the symbols in the formula have the same meanings as in 10)above) to obtain a lithium compound represented by general formula(VIII)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -A).sub.n !.sup.-  Li!.sup.+                                        (VIII)

(wherein A is hydrogen or bromine chemically bonded to R⁴);

(c) lithionating the compound of general formula (VIII) with an organiclithium and then reacting with a silicon compound represented by generalformula (VI) or (VII) below:

    SiR.sup.5 R.sup.6 R.sup.7 R.sup.13                         (VI)

    R.sup.8 R.sup.9 R.sup.10 SiYSiR.sup.11 R.sup.12 R.sup.14   (VII)

(wherein the symbols in the formulae have the same meanings as in 10)above) to obtain a compound represented by general formula (IX)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -L).sub.n !.sup.-  Li!.sup.+                                        (IX)

(wherein L has the same meaning as in 1) above and other symbols in theformula have the same meanings as above); and

(d) reacting the compound of general formula (IX) with a halide of amonovalent cation.

12) The method of producing the ionic compounds as described in 10) or11) above, wherein the compound of general formula (IV) is a compoundrepresented by general formula (IVa) ##STR1## (wherein the symbols inthe formula have the same meanings as in 10) above).

13) A Catalyst component for olefin polymerization comprising the ioniccompound described in 1) above chemically bonded to a carrier.

14) The catalyst component as described in 13) above, wherein thecarrier is a solid having a functional group represented by generalformula (X)

    --OR                                                       (X)

(wherein R is a hydrogen atom, a C₁ -C₂₀ alkyl group, alkali metal oramine).

15) The catalyst component as described in 14) above, wherein thecarrier is a solid having a hydroxyl group.

16) The catalyst component as described in 13) above, wherein thecarrier is silica, alumina or mixtures thereof.

17) A catalyst for olefin polymerization comprising the following asessential components:

(a) the catalyst component for olefin polymerization as described in 13)above,

(b) an organometal compound, and

(c) a Group 4, 5 or 6 transition metal compound.

18) The catalyst as described in 17) above, wherein the Group 4, 5 or 6transition metal compound is metallocene.

DETAILED DESCRIPTION OF THE INVENTION

Hereafter, this invention will be described in detail.

IONIC COMPOUND!

The ionic compound which can be used in this invention includes thosecompounds represented by the following general formula (I):

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -L).sub.n !.sup.-  D!                                               +(I)

wherein M is a Group 13 metal. Preferred examples of M include boron andaluminum, with boron being particularly preferred.

R¹, R² and R³ (each bonded to M), which may be the same or different,are selected from a C₁ -C₂₀ hydrocarbyl group, substituted hydrocarbylgroup, or alkoxide group or a halogen atom. These are preferably a C₁-C₂₀ aromatic hydrocarbyl group, halogen-substituted aromatichydrocarbyl group, or halogenated hydrocarbon-substituted aromatichydrocarbyl group, and more preferably a phenyl group, a 2-fluorophenylgroup, a 3-fluorophenyl group, a 4-fluorophenyl group, a2,4-difluorophenyl group, a 2,5-difluorophenyl group, a3,5-difluorophenyl group, a 3,4,5-trifluorophenyl group, a2,3,4,5-tetrafluorophenyl group, a pentafluorophenyl group, or a3,5-bis(trifluoromethyl)phenyl group, with a pentafluorophenyl groupbeing most preferred.

k, l and m are each 0 or an integer of 1 to 3, provided that they have arelation with n described below such that k+l+m+n=4.

R⁴ (bonded to M) represents a C₁ -C₂₀ alkylene group, substitutedalkylene group, substituted phenylene group, silanylene group,substituted silanylene group, silalkylene group, substituted silalkylenegroup, oxasilanylene group, substituted oxasilanylene group, oroxasilalkylene group.

The present inventors confirmed that the substituent groups ofparticularly the substituted phenylene group represented by R⁴ giveimportant influence to the activity of the catalyst and the propertiesof the resulting polymer and that preferred substituents for phenyleneare halogens and halogenated hydrocarbons. Preferred substitutedphenylene groups include 2-fluorophenyl group, 3-fluorophenyl group,2,5-difluorophenyl group, 3,5-difluorophenyl group,2,3,5-trifluorophenyl group, 3,5-bis(trifluoromethyl)phenylene group,2,3,5,6-tetrafluorophenyl group, among which 2,3,5,6-tetrafluorophenylgroup is particularly preferred.

L (bonded to R4) is a carrier bondable functional group. The carrierbondable functional group is a functional group which can form achemical bond with a surface of a carrier. For example, when there is ahydroxyl group on the surface of a carrier, a compound having achlorosilyl group can form a silicon-oxygen bond by a reaction with thehydroxyl group. In this case, the chlorosilyl group is a carrierbondable functional group. More specifically, the carrier bondablefunctional group includes those functional groups represented by generalformulae (II) or (III) below:

    SiR.sup.5 R.sup.6 R.sup.7                                  (II)

    R.sup.8 R.sup.9 R.sup.10 SiYSiR.sup.11 R.sup.12            (III)

(wherein R⁵ to R¹² (each bonded to Si), which may be the same ordifferent, represent each a C₁ -C₂₀ hydrocarbyl group, substitutedhydrocarbyl group, or alkoxide group, or a halogen atom, with at leastone of R⁵, R⁶ and R⁷ and at least one of R⁸, R⁹ and R¹⁰ being a halogenatom;

Y is --O--, a C₁ -C₂₀ alkylene group, substituted alkylene group,phenylene group, substituted phenylene group, or a group represented byformula:

    --(Z.sup.1 SiZ.sup.2 Z.sup.3 Z.sup.4).sub.r --

(wherein Z¹ and Z⁴, which may be the same or different, represent eachan alkylene group, a substituted alkylene group, a phenylene group, asubstituted phenylene group, --O--, an oxyalkylene group, a substitutedoxyalkylene group, an oxyphenylene group, or a substituted oxyphenylenegroup; Z² and Z³, which may be the same or different, represent each ahydrogen atom, an alkyl group, a substituted alkyl group, a phenylgroup, or a substituted phenyl group; r is an integer of at least 1).

Specific examples of L include a trichlorosilyl group, amethyldichlorosilyl group, a dimethylchlorosilyl group, anethyldichlorosilyl group, a diethylchlorosilyl group, aphenyldichlorosilyl group, a diphenylchlorosilyl group, atrimethoxysilyl group, a methyldimethoxysilyl group, adimethylchlorosilyl group, an ethyldimethoxysilyl group, adiethylmethoxysilyl group, a triethoxysilyl group, a methyldiethylsilylgroup, a dimethylethoxysilyl group, an ethyldiethoxysilyl group, adiethylethoxysilyl group, a phenyldiethoxysilyl group, adiphenylethoxysilyl group, a trihydroxysilyl group, adihydroxyphenylsilyl group, a 2-(dimethylchlorosilyl)ethyldimethylsilylgroup, a 6-(dimethylchlorosilyl)hexyldimethylchlorosilyl group, a8-(dimethylchlorosilyl)octyldimethylchlorosilyl group, a2-(trichlorosilyl)ethyldichlorosilyl group, a6-(trichlorosilyl)hexyldichlorosilyl group, a8-(trichlorosilyl)octyldichlorosilyl group, etc. of these, atrichlorosilyl group, a trimethoxysilyl group, triethoxysilyl group, atrihydroxysilyl group, a dimethylchlorosilyl group, adimethylmethoxysilyl group, a dimethylethoxysilyl group, adimethylhydroxysilyl group, a methyldichlorosilyl group, amethyldimethoxysilyl group, a methyldiethoxysilyl group, and amethyldihydroxysilyl group are preferred, with a trichlorosilyl group, amethyldichlorosilyl group, and a dimethylchlorosilyl group beingparticularly preferred.

n is an integer of 1 to 4, and when n is 2 or more, R⁴ -L's may be acombination of different groups.

D represents a monovalent cation, which means carbonium, anilinium,ammonium, ferrocenium, phosphonium, sodium, potassium, lithium, etc.

Specific examples of D include trimethylammonium, triethylammonium,tripropylammonium, tributylammonium, N,N-dimethylammonium,N,N-diethylammonium, N,N-2,4,5-pentamethylanilinium,triphenylphosphonium, tri(p-tolyl)phosphonium, triphenylcarbenium, etc.Of these, N,N-dimethylanilinium and triphenylcarbenium are preferred.

Specific examples of such an ionic compound includeN,N-Dimethylanilinium salts, for example, the following compounds.

N,N-Dimethylanilinium tris(pentafluorophenyl)p-trichlorosilyltetrafluorophenylborate,

N,N-Dimethylanilinium tris(pentafluorophenyl)p-methyldichlorosilyltetrafluorophenylborate,

N,N-Dimethylanilinium tris(pentafluorophenyl)p-dimethylchlorosilyltetrafluorophenylborate,

N,N-Dimethylanilinium tris(pentafluorophenyl)p-trimethoxysilyltetrafluorophenylborate,

N,N-Dimethylanilinium tris(pentafluorophenyl)p-dimethoxymethylsilyltetrafluorophenylborate,

N,N-Dimethylanilinium tris(pentafluorophenyl)p-methoxydimethylsilyltetrafluorophenylborate,

N,N-Dimethylanilinium tris(pentafluorophenyl)p-triethoxysilyltetrafluorophenylborate,

N,N-Dimethylanilinium tris(pentafluorophenyl)p-diethoxymethylsilyltetrafluorophenylborate,

N,N-Dimethylanilinium tris(pentafluorophenyl)p-ethoxydimethylsilyltetrafluorophenylborate,

N,N-Dimethylanilinium tris(pentafluorophenyl)p-trihydroxysilyltetrafluorophenylborate,

N,N-Dimethylanilinium tris(pentafluorophenyl)p-dihydroxymethylsilyltetrafluorophenylborate,

N,N-Dimethylanilinium tris(pentafluorophenyl)p-hydroxydimethylsilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-trichlorosilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-methyldichlorosilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-dimethylchlorosilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-trimethoxysilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-dimethoxymethylsilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-methoxydimethylsilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-triethoxysilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-diethoxymethylsilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-ethoxydimethylsilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-trihydroxysilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-dihydroxymethylsilyltetrafluorophenylborate,

Triphenylcarbenium tris(pentafluorophenyl)p-hydroxydimethylsilyltetrafluorophenylborate,

Of these ionic compounds, preferred are N,N-dimethylaniliniumtris(pentafluorophenyl)4-(trichlorosilyl)-2,3,5,6-tetrafluorophenylborate,N,N-dimethylanilinium tris(pentafluorophenyl)4-(methyldichlorosilyl)-2,3,5,6-tetrafluorophenylborate, andN,N-dimethylanilinium tris(pentafluorophenyl)4-(dimethylchlorosilyl)-2,3,5,6-tetrafluorophenylborate.

Production Method for Ionic Compounds!

The ionic compounds of this invention can be produced using thefollowing compounds.

(1) A compound represented by general formula (IV):

    X.sup.1 -R.sup.4 -X.sup.2                                  (IV)

(wherein X¹ and X² independently represent a hydrogen atom or a bromineatom, and R⁴ has the same meaning as above);

(2) A compound represented by general formula (V):

    MR.sup.1 R.sup.2 R.sup.3                                   (V)

(wherein M, R¹, R² and R³ have the same meanings as above);

(3) A compound represented by general formula (VI) or (VII):

    SiR.sup.5 R.sup.6 R.sup.7 R.sup.13                         (VI)

    R.sup.8 R.sup.9 R.sup.10 SiYSiR.sup.11 R.sup.12 R.sup.14   (VII)

(wherein R⁵ to R¹² have the same meanings as above, and R¹³ and R¹⁴independently represent a C₁ -C₂₀ hydrocarbyl group, substitutedhydrocarbyl group, alkoxide group, or a halogen atom); and

(4) A halide of a monovalent cation.

As the reaction process for producing these compounds, there may beconsidered various reaction procedures. However, any process may be usedas far as there can finally be obtained compounds represented by generalformula (I)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -L).sub.n !.sup.-  D!.sup.+                                         (I)

(wherein the symbols in the formula have the same meanings as above).

As the most typical process, there can be cited a reaction processincluding the following steps (a) to (d). This reaction process,described briefly, comprises the steps of activating a compoundcontaining a R⁴ group (first step), bonding the compound with a compoundcontaining a Group 13 element (M) (second step), introducing a carrierbondable functional group to the resulting compound (L) (third step),and then forming a salt with a cation D!⁺ (fourth step).

Hereafter, each of the steps is described in detail.

(a) First step:

Bromines or hydrogens in a compound represented by general formula (IV)

    X.sup.1 -R.sup.4 -X.sup.2                                  (IV)

(wherein X¹ and X² are bromine or hydrogen provided that for compoundshaving low acidities, at least one of the symbols must be bromine) aresubstituted by lithium (lithionated) with an organic lithium.

The lithionation can be performed by a conventional method. Morespecifically, the compound of formula (IV) above and an organic lithiumcompound are mixed in a nonreactive solvent to allow reactiontherebetween.

The compound of formula (IV) is selected depending on final targetcompound and is preferably a halogenated aryl or a halogenatedhydrocarbon-substituted aryl as described above. Particularly preferredare tetrafluoro-mono- (or -di)-bromobenzene represented by the followingformula (IVa) ##STR2##

Any organic lithium compounds may be used without limitation as far asthey are commonly used for lithionation. For example, there can be citedn-butyllithium, t-butyllithium, and phenyllithium. It is preferred thatthese are dissolved in an inert solvent such as hexane before they canbe subjected to lithionation. Preferred reaction solvents include etherbased solvents such as diethyl ether and tetrahydrofuran.

The reaction between the compound of formula (IV) and the organiclithium compound can be performed in proportions of about 1:1 to 1:10(by mole), and preferably 1:1 (by mole). The reaction temperature is-100° to 0° C., and preferably -80° to -20° C. It is preferred to allowthe reaction to proceed gently by adding the organic lithium compound inportions. The reaction time lasts preferably for 30 minutes or longer.

(b) Second step: Formation of a salt containing a Group 13element-containing compound

The lithium substituted compound obtained in the first step is reactedwith a Group 13 element-containing compound represented by generalformula (V)

    MR.sup.1 R.sup.2 R.sup.3                                   (V)

(wherein the symbols in the formula have the same meanings as above) toobtain a lithium compound represented by general formula (VIII)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -A).sub.n !.sup.-  Li!.sup.+                                        (VIII)

(wherein A is hydrogen or bromine).

In the formula (V) above, M is a Group 13 element, among which preferredare boron and aluminum, with particularly preferred being boron. In thesame formula, R¹, R² and R³, which may be the same or different, may bea C1-C20 hydrocarbyl group, substituted hydrocarbyl group, or alkoxidegroup, or a halogen atom. Preferably, they represent a phenyl group, a2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a2,4-difluorophenyl group, a 2,5-difluorophenyl group, a3,5-difluorophenyl group, a 3,4,5-trifluorophenyl group, a2,3,4,5-tetrafluorophenyl group, a pentafluorophenyl group, a3,5-bis(trifluoromethyl)phenyl group, with a pentafluorophenyl groupbeing particularly preferred.

This reaction can be performed by mixing the lithionated compoundobtained in the first step with a solution of the compound of generalformula (V) in a solvent in proportions such that the molar ratio of thelithionated compound to the compound of general formula (V) is 1.0 ormore. Preferred mixing ratio is 1.0 to 2.0. When the lithionatedcompound is added, it is preferred that the temperature of the solutionis kept low. More specifically, the temperature is -100° to 50° C., andpreferably -20° to 30° C. As for the solvent for dissolving the compoundof general formula (V), there can be used liquids which are nonreactivewith the lithionated compound and the compound of general formula (V).Preferred solvent includes C₁₀ -C₂₀ hydrocarbons and ethers.Particularly preferred ones are toluene, heptane, decane, isoparaffin,diethyl ether, and tetrahydrofuran. The reaction time is preferably 30minutes or longer. It is preferred that after the reaction, unreactedmaterials are removed by washing or the like. The compound of generalformula (V) may be used in the state where a solvent such as ether isadded.

(c) Third step: Introduction of Carrier Bondable Functional Group

The compound of general formula (VIII) is lithionated with an organiclithium and then reacted with a silicon compound represented by generalformula (VI) or (VII) below

    SiR.sup.5 R.sup.6 R.sup.7 R.sup.13                         (VI)

    R.sup.8 R.sup.9 R.sup.10 SiYSiR.sup.11 R.sup.12 R.sup.14   (VII)

(wherein R⁵ to R¹² have the same meanings as above, and R¹³ and R¹⁴independently represent a C₁ -C₂₀ hydrocarbyl group, substitutedhydrocarbyl group, alkoxide group, or a halogen atom) to obtain acompound represented by general formula (IX)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -L).sub.n !.sup.-  Li!.sup.+                                        (IX)

(wherein the symbols in the formula have the same meanings as above).

The mixing ratio of the compound of general formula (VIII) and thesilicon compound, as molar ratio of the latter to the former, is 1 foldto 100 folds, preferably 2 folds to 20 folds. Stirring is performed fora certain time at room temperature to complete the reaction. Thereafter,a hydrocarbon having a boiling point higher than the solvent is added tothe reaction mixture, the reaction solvent is distilled off, and thehydrocarbon solvent is removed. After washing with the hydrocarbonsolvent, the washing solvent is removed. The compound thus obtained isdissolved in a solvent such as dichloromethane.

(d) Fourth step: Cation Exchange Reaction

Finally, the compound of general formula (IX) is reacted with a halideof a cation D to yield a target ionic compound represented by generalformula (I)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -L).sub.n !.sup.-  D!.sup.+                                         (I)

(wherein the symbols in the formula have the same meanings as above).

The halide of D is a compound which generates a monovalent cation D whenreacted with the compound of general formula (IX) above. Morespecifically, the halide of D includes trimethylamine hydrochloride,triethylamine hydrochloride, tripropylamine hydrochloride, tributylaminehydrochloride, N,N-dimethylaniline hydrochloride, N,N-diethylaminehydrochloride, N,N-2,4,5-pentamethylaniline hydrochloride,triphenylphosphine hydrochloride, triphenylchloromethane and the like.Of these, preferred are N,N-dimethylaniline hydrochloride andtriphenylchloromethane.

The reaction can be performed at -100° to 200° C., preferably at 20° to150° C. The reaction time is preferably 1 hour or longer. Lithium halideprecipitates and removal of which yields the target compound. Thecompound can be used in a state of solution or in a state of solid afterdrying.

Catalyst Component for Olefin Polymerization!

Next, description will be made of the catalyst component for olefinpolymerization, comprising the ionic compound of this inventionchemically bonded to a carrier.

In this invention, by the term "chemical bonds" is meant covalent bonds,ionic bonds, metal bonds, and coordination bonds.

(1) Carrier

In this invention, by the term "carrier" is meant a solid which has asurface with which a plurality of the ionic compounds of this inventioncan form chemical bonds, the surface having an area and properties suchthat upon polymerization reaction, a plurality of polymerization activesites can be formed.

As the carrier, there can be used inorganic oxides, inorganic chlorides,inorganic hydroxides, organic high molecular weight compounds. Morespecifically, there can be used one or more members selected from thegroup consisting of inorganic compounds such as silica, alumina,silica-alumina, magnesia, titania, zirconia, and calcia, polymers ofvinyl chloride, vinyl alcohol, methacrylic acid, acrylic acid and thelike, or copolymers thereof with styrene, divinylbenzene or the like,and homopolymer or copolymer of α-olefins chemically modified to have afunctional group which can react with a carrier bondable functionalgroup of the ionic compound to form a chemical bond to the ioniccompound. It is preferred to use one or more of silica, alumina orsilica-alumina.

Among the carriers, preferred are those having a functional grouprepresented by general formula (x)

    --OR                                                       (X)

on the surface of the carrier.

In the above formula, R represents hydrogen, a C₁ -C₂₀ alkyl group,alkali metal or amine. Of these, preferred are hydrogen, a methyl group,an ethyl group, sodium and lithium, with hydrogen being most preferred.

The carrier in this invention requires large surface area and porediameter and functional groups on the surface for chemically modifyingthe surface with an ionic compound. Further, the ionic compound borneform polymerization active species by forming ion pairs with thetransition metal compound so that the carrier must have space forforming such ion pairs. In addition, polymerization activity percatalyst is higher, the larger the amount of the ion pair formed on thecarrier and, hence, it is desired that the carrier have a large surfacearea and a large average pore diameter. As the carrier in thisinvention, it is preferred to use fine particles having an averageparticle diameter of 5 to 200 μm, a specific surface area of 100 to1,000 m² /g, and an average pore diameter of 20 Å or more.

(2) Reaction of the Ionic Compound with the Carrier

The reaction between the carrier in this invention and the ioniccompound having a carrier bondable functional group can be performed byvarious methods. Generally, the reaction is performed in organicsolvents. More specifically, there can be used aliphatic hydrocarbonssuch as pentane, hexane, heptane, octane, nonane, and decane, alicyclichydrocarbons such as methylcyclopentane, cyclopentane, and cyclooctane,aromatic hydrocarbons such as benzene, toluene, xylene, cumene, andcymene, aliphatic halogenated hydrocarbons such as chloroform anddichloromethane, aromatic halogenated hydrocarbons such aschlorobenzene, and dichlorobenzene, alcohols such as methanol andethanol, ethers such as diethyl ether and tetrahydrofuran, and the like.

Although the reaction between the carrier and the ionic compound havinga carrier bondable functional group can be under any conditions as faras the target bond is formed, generally the following conditions aredesirable.

The reaction temperature is usually -70° C. to 200° C., and preferably0° C. to 150° C. It is preferred that the reaction between the ioniccompound having a carrier bondable functionality with the functionalgroup on the surface of the carrier proceed sufficiently.

The reaction time may vary depending on the concentration, temperatureand other conditions and is not limited generally. Usually, the reactioncan proceed for 1 to 50 hours.

The reaction for bonding can be carried out at a concentration of theionic compound in the reaction solvent being 1 to 10,000 ppm and at aconcentration of the carrier being 1 to 50 wt. %.

There is no particular limitation in the proportion of amounts of theionic compound having a carrier bondable functional group and of thecarrier. When the number of the functional groups on the surface of thecarrier is equal to or greater than the equivalent the carrier bondablefunctional group, unreacted functional groups on the surface of thecarrier will react with the transient metal compound so that there isthe possibility that no polymerization active species can be formed. Inthis case, the reaction with the transient metal compound can beprevented from occurring by reacting the functional group on the surfaceof the carrier with a different compound. For example, where theunreacted functional group is a hydroxyl group, treatment of thehydroxyl group with trimethylchlorosilane or the like results in theprevention of the reaction between the transient metal compound and theunreacted functional group on the surface of the carrier.

The catalyst component for olefin polymerization, the reaction product,is separated from the reaction mixture and the ionic compounds havingunreacted carrier bondable functional groups are removed by washing. Asthe solvent for washing, there can be used the above-described organicsolvents. The temperature for washing is -30° C. to 120° C., andpreferably 0° C. to 100° C. Preferably, the washing is continued untilthe ionic compound having a carrier bondable functional group cannotdetected substantially in the washings. After completion of the washing,the solid component carrying the ionic compounds is dried or may be usedin the presence of an organic solvent.

Formation of chemical bonds between the ionic compound having a carrierbondable functional group and the carrier can be confirmed bydetermination of a reduction in the amount of the functional group onthe carrier as a result of the reaction or by determination of theamount of the compound which is formed as a result of the reactionbetween the functional group on the surface of the carrier and thecarrier bondable functional group of the ionic compound. Alternatively,such is confirmed by detecting IR absorption and NMR peaks of new bondswhich are formed as a result of the reaction.

Catalyst for Olefin Polymerization!

Next, description will be made of the catalyst for olefin polymerizationof this invention.

The component for olefin polymerization catalyst is characterized byusing

(a) a component of olefin polymerization catalyst in which the ioniccompound is chemically bonded to the carrier,

(b) an organometal compound, and

(c) a Group 4, 5 or 6 transtion metal compound.

Of these, (a) has already been described above.

In the organometal compound (component (b)) which is one of the catalystcomponent for olefin polymerization in this invention, the metal elementis generally lithium, sodium, magnesium, aluminum, tin, zinc ortitanium. The organic group which combines with the metal to form anorganic metal compound generally includes an alkyl group (C₁ -C₁₀), anda phenyl group, a cyclopentadienyl group or derivatives thereof.

At least one of the valence of the above-described metal element must besatisfied with the above-described organic group while the rest valencesmay be satisfied with other atoms or atomic groups. Such atoms or atomicgroups may be, for example, a halogen atom, a hydrogen atom, an alkoxygroup, etc.

As such organic compounds, there can be cited, for example,organolithium compounds such as n-butyllithium, t-butyllithium, andphenyllithium, organosodium compounds such as cyclopentadienylsodium andmethylsodium, organomagnesium compounds such as butylethylmagnesium,butyloctylmagnesium, ethylmagnesium bromide, and butylmagnesium bromide,organoaluminum compounds such as trimethylaluminum, triethylaluminum,triisobutylaluminum, diethylaluminum halide, diethylaluminum chloride,diethylaluminum bromide, diethylaluminum ethoxide, ethylaluminumsesquichloride, and isobutylaluminoxane, organotin compounds such astetraethyltin, tetrabutyltin, tributyltin chloride, and tetraphenyltin,organozinc compounds such as diethylzinc, and dibutylzinc,organotitanium compounds such as dicyclopentadientyltitanium dimethyl.Of these, preferred are oragnoaluminum compounds and organomagnesiumcompounds.

In the catalyst for olefin polymerization of this invention, theorgaometal compound component may be used as a combination of two ormore of them.

The Group 4, 5 or 6 transtion metal compound (component (c)), one of thecomponents for olefin polymerization catalyst, is preferably a transtionmetal compound represented by general formulae (XI), (XII) or (XIII)below ##STR3## wherein R¹⁵ to R²⁴, which may be the same or different,represent each a hydrogen atom or a hydrocarbyl group (C₁ -C₂₀ alkyl,alkenyl, aryl, alkylaryl, arylalkyl or the like), an alkylsilyl group,an alkylgermyl group, or a 4-6 membered ring having a carbon-carbonbond, which may be the same or different, R²⁵ represents a C₁ -C₂₀alkylene group, an alkylgermylene or alkylsilylene,

a plurality of Q¹ s, and Q² and Q³, which may be the same or different,represent each a C_(1-C) ₂₀ aryl, alkyl, alkenyl, alkylaryl, arylalkylor the like hydrocarbyl group, alkoxy, alkoxy, siloxy, hydrogen orhalogen, Ya is an electron donating ligand selected from --O--, --S--,--NR²⁶ --, --PR²⁶ --, or --OR²⁶, --SR²⁶, --NR²⁶ R²⁷, and --PR²⁶ R²⁷ (R²⁶and R²⁷ represent each hydrogen or a C₁ -C₂₀ alkyl, alkenyl, aryl,alkylaryl, arylalkyl or the like hydrocarbyl group, or halogenated alkylor halogenated aryl), Me is a transtion metal of Group 3, 4, 5 and 6 ofthe periodic table, p is 0 or 1!.

In the above formulae, the transtion metal elements of Group 4, 5 and 6of the periodic table (Group being after 1990 Rule of Inorganic CompoundNomenclature) are preferably selected from the transtion metal elementsof Group 4 of the periodic table, i.e., titanium, zirconium, andhafnium, with particularly preferred being zirconium and hafnium.

In the above formulae, the hydrocarbyl group represented by R¹⁵ to R²⁴include, for example, a methyl group, an ethyl group, a propyl group, abutyl group, an isobutyl group, a t-butyl group, an amyl group, anisoamyl group, a hexyl group, a heptyl group, an octyl group, a nonylgroup, a decyl group, a cetyl group, a phenyl group, etc., thealkylsilyl group includes a trimethylsilyl group, etc., the alkylgermylgroup includes a trimethylgermyl group, etc. As the cyclopentadienylligand, there can be cited, for example, alkyl substitutedcyclopentadienyl group such as a cyclopentadienyl group, amethylcyclopentadienyl group, an ethylcyclopentadienyl group, ann-butylcyclopentadienyl group, a t-butylcyclopentadienyl group, atrimethylsilylcyclopentadienyl group, a dimethylcyclopentadienyl group,a pentamethylcyclopentadienyl group, and an indenyl group, a fluorenylgroup and the like having or not having similar substituents.

In the above formulae, as the alkylene group represented by R²⁵, therecan be cited, for example, a methylene group, an ethylene group, apropylene group, an isopropylidene group, a cyclopentylidene group, acyclohexylidene group, a tetrahydropyran-4-ylidene group, adiphenylmethylene group, etc. As the alkylsilylene group, there can becited, for example, a dimethylsilylene group, a diphenylsilylene group,etc. As the alkylgermylene group, there can be cited, for example, adimethylgermylene group, a diphenylgermylene group, etc.

In the above formulae, specific examples of R²⁶ and R²⁷ in Ya include amethyl group, an ethyl group, a propyl group, a butyl group, an isobutylgroup, a t-butyl group, an amyl group, an isoamyl group, a hexyl group,a heptyl group, an octyl group, a nonyl group, a decyl group, a cetylgroup, a phenyl group, a benzyl group, etc.

In Ya, ligands of the type --NR²⁶ -- or --PR²⁶ -- are preferred.

Hereafter, specific examples of the transtion metal compound representedby general formulae (XI), (XII) or (XIII) when Me is zirconium areexemplified.

Examples of the transtion metal compounds represented by general formula(XI) include:

Biscyclopentadienylzirconium dichloride,

Bis(methylcyclopentadienyl)zirconium dichloride,

Bis(n-butylcyclopentadienyl)zirconium dichloride,

Bis (n-butylcyclopentadienyl) zirconium dimethyl,

Bis (1, 3-dimethylcyclopentadienyl) zirconium dichloride,

Bis(pentamethylcyclopentadienyl)zirconium dichioride,

(Cyclopentadienyl)(methylcyclopentadienyl) zirconium di chloride,

(Cyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride,

(Cyclopentadienyl)(indenyl)zirconium dichloride,

(Cyclopentadienyl)(fluorenyl)zirconium dichloride,

Cyclopentadienylzirconium trichloride,

Cyclopentadienylzirconium trimethyl,

Pentamethylcyclopentadienylzirconium trichloride,

Pentamethylcyclopentadienylzirconium trimethyl, etc.

Examples of the transtion metal compound represented by general formula(XII) include:

Dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride,

Isopropylidenebis(methylcyclopentadienyl) zirconium dichloride,

Ethylenebis(indenyl)zirconium dichloride,

Ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride,

Isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

Isopropylidene(cyclopentadienyl)(indenyl)zirconium dichloride,

Isopropylidene(t-butylcyclopentadienyl) t-butylindenyl)zirconiumdichloride,

Isopropylidene(t-butylcyclopentadienyl)(t-butylindenyl)zirconiumdimethyl,

Dimethylsilylene-bis{1-(2-methyl-4-benzoindenyl)}-zirconium dichloride,

Dimethylsilylene-bis{1-(2-methyl-4-phenylindenyl)}-zirconium dichloride,

Dimethylsilylene-bis{1-(2-methyl-4-naphthylindenyl)}-zirconiumdichloride, etc.

Examples of the transtion metal compound represented by general formula(XIII) include:

Ethylene(t-butylamide)(tetramethylcyclopentadienyl)-zirconiumdichloride,

Ethylene(methylamide)(tetramethylcyclopentadienyl)-zirconium dichloride,

Dimethylsilylene(t-butylamide)(tetramethyl-cyclopentadienyl)zirconiumdichloride,

Dimethylsilylene(t-butylamide)(tetramethyl-cyclopentadienyl)zirconiumdibenzyl,

Dimethylsilylene(benzylamide)(tetramethyl-cyclopentadienyl)zirconiumdibenzyl,

Dimethylsilylene(phenylamide)(tetramethyl-cyclopentadienyl)zirconiumdichloride, etc.

Herein, the zirconium compounds were exemplified by referring to theirspecific names. Also, those transtion metal compounds in which zirconiumis replaced by hafnium or titanium are useful in this invention.

Regarding the use of the transtion metal compounds according to thisinvention, the above-described transtion metal compounds can be usedsingly or two or more of them may be used in combination.

Molar ratio of the transtion metal compound and the Group 13 element inthe components (a), (b) and (c) for olefin polymerization in thisinvention is such that upon polymerization, the transtion metal is 0.01to 10 times, preferably 0.1 to 1 time, as much as the Group 13 element.The concentration of the transient metal compound upon polymerizationcan be 0.01 to 100 ppm, preferably 0.1 to 10 ppm.

The catalyst for olefin polymerization of this invention can be used bycontacting (a), (b) and (c) recited in the claims in a solvent or in thepresence of a monomer. Methods for contacting the components are notlimited particularly. However, a method is preferred in which thecomponent (a) is contacted with the component (b) in an inert solventand then mixed with the component (c).

Also, after the components (a), (b) and (c) are contacted, the solventmay be distilled off. Alternatively, the mixture may be washed with asolvent such as a hydrocarbon and can be used as a slurry or the solventmay be distilled off thereafter.

The catalyst thus prepared is charged in a polymerization apparatus. Inthis case, it is preferred that the above-described organometal compoundis charged in the polymerization reactor in advance. Particularly whenno washing with a hydrocarbon solvent is performed, it is preferred tocharge the organometal compound (e.g., organolithium compound) in thepolymerization reactor in advance.

Polymerization of Olefins Using the Catalyst!

In this invention, methods and conditions of polymerization using theabove-described catalyst are not limited particularly and there can beused, for example, solution polymerization methods, melt polymerizationmethods, slurry polymerization methods, suspension polymerizationmethods, gas phase polymerization methods and the like. This inventionis effective particularly for processes in which polymers arenon-homogeneous. More specifically, slurry methods and gas phase methodsare exemplified.

The polymerization temperature is within the ranges of -100° to 300° C.,and preferably 0° to 150° C., and the polymerization pressure is withinthe ranges of atmospheric pressure to 100 kg/cm², and preferablyatmospheric pressure to 50 kg/cm². The polymerization reaction may beany of batch methods, semi-continuous methods, and continuous methods.Further, multi-step polymerization can also be performed.

The molecular weight of the resulting polymer can be controlled by useof a chain transfer agent such as hydrogen or polymerizationtemperature.

In this invention, as the hydrocarbon solvent which can be used in thepolymerization, there can be cited, for example, aliphatic hydrocarbonssuch as propane, butane, isobutane, pentane, hexane, heptane, octane,nonane, and decane, alicyclic hydrocarbons such as methylcyclopentane,cyclopentane, and cyclooctane, aromatic hydrocarbons such as benzene,toluene, xylene, cumene and cymene. These solvents may be used singly ortwo or more of them can be used in admixture.

As the olefin to be used for polymerization, there can be cited, forexample, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene,4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cycloheptene,norbornene, 5-methyl-2-norbornene, tetracyclododecene, etc. Further,there can be cited, for example, styrene, vinylcyclohexane,vinylcyclohexene, divinylbenzene, dienes, etc.

In this invention, not only homopolymerization of olefins can beperformed but also copolymers of, for example, ethylene with propylene,ethylene with 1-butene, and the like can be produced.

In the polymerization method of this invention, preliminarypolymerization can be performed using the catalyst of this invention.There is no particular limitation on the method of the preliminarypolymerization but known methods can be used therefor. Olefins to beused for preliminary polymerization are not limited particularly and theabove-described olefins can be used. The temperature for preliminarypolymerization is usually -20° to 300° C., preferably -10° to 200° C.,and more preferably 0° to 100° C. As the solvent, there can be usedinert hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons,monomers and the like. Preferred are aliphatic hydrocarbons. Also, thepreliminary polymerization can be performed without solvents.

The catalyst containing the ionic compound carrying carrier of thisinvention has high activity so that polymerization of olefins by aslurry process, a gas phase process or the like using the catalyst givesrise to a polymer having good powder characteristics and attachment ofthe polymer to the reactor is minimized.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereafter, this invention will be described in more detail by examplesand comparative examples. However, this invention is not limited to theexamples. In the following examples, "%" is by weight unless otherwiseindicated specifically.

EXAMPLE 1 Production of Dimethylanilinium4-trichlorosilyl-2,3,5,6-tetrafluorophenyltris(pentafluorophenyl)borateIonic Compound!

3.85 Grams (1.86 mmol) of 1-bromo-2,3,5,6-tetrafluorobenzene wasdissolved in 50 ml of diethyl ether and cooled in a dry ice/denaturedalcohol bath. To the solution was added dropwise 10.5 ml of a solutionof 1.6 mol of n-butyllithium/liter of hexane, followed by stirring for30 minutes to prepare a lithionated product of1-bromo-2,3,5,6-tetrafluorobenzene (2,3,5,6-tetrafluoropheny-lithium).

The reaction mixture containing the above-described lithionated compoundwas added to 200 ml of a hexane solution containing 5.07 g (9.9 mmol) oftris(pentafluorophenyl)borane, and stirred at 25° C. for 20 minutes toprecipitate product (A). The solution layer was removed and vacuum driedafter it was washed with hexane.

1.66 Grams of the product (A) was dissolved in 10 ml of tetrahydrofuranand cooled in a dry ice/denatured alcohol bath. To this solution wasadded dropwise 1.5 ml of a solution of 1.6 mol of n-butyllithium/literof hexane, followed by stirring for 45 minutes. Thereafter, the solutionwas added to a solution of 2.7 ml of silicon tetrachloride in 10 ml oftetrahydrofuran, and the mixture was stirred at 25° C. for 15 minutes.Further, 100 ml of heptane was added and tetrahydrofuran was distilledoff. The heptane layer was removed and dried under vacuum after it waswashed with hexane. The product was dissolved in 50 ml ofdichloromethane and after lithium chloride which precipitated wasremoved, the product was dried under vacuum to yield 1.65 g of product(B).

1.65 Grams of product (B) was dissolved in 30 ml of dichloromethane and0.31 g of dimethylanilinium chloride was added, and the mixture wasstirred at 25° C. for 5 minutes. Lithium chloride which precipitated wasremoved and the product was dried under vacuum to yield 1.7 g ofdimethylanilinium4-trichlorosilyl-2,3,5,6-tetrafluorophenyltris(pentafluorophenyl)borate.Its chemical structure was confirmed by NMR data measured (a part ofwhich is shown below).

¹ H-NMR (CD₂ Cl₂): δ3.23(6H), 7.50(2H) , 7.57(3H), 11.5(1H);

¹⁹ F-NMR (CD₂ Cl₂): δ-131.0, -131.6, -132.9, -163.4, -167.3

EXAMPLE 2 Production of Dimethylanilinium4-dimethylchlorosilyl-2,3,5,6-tetrafluorophenyltris(pentafluorophenyl)borateIonic Compound!

7.5 Grams (50 mmol) of 1,2,4,5-tetrafluorobenzene was dissolved in 50 mlof diethyl ether and cooled in a dry ice/denatured alcohol bath. To thesolution was added dropwise 31.3 ml of a solution of 1.6 mol ofn-butyllithium/liter of hexane, followed by stirring for 30 minutes. Theresulting solution was added to 883 ml (50 mmol) of 2.9% isoparaffinsolution of tris(pentafluorophenyl)borane, and stirred at 25° C. for 30minutes. Upon this, product (C) precipitated. The solution layer wasremoved and washed with hexane, followed by drying under vacuum. Theproduct (C) was recrystallized from diethyl ether (yield: 34.5 g).

8.44 Grams (9.5 mmol) of the product (C) was dissolved in 30 ml oftetrahydrofuran and cooled in a dry ice/denatured alcohol bath. To thissolution was added dropwise 6.25 ml of a solution of 1.6 mol ofn-butyllithium/liter of hexane, followed by stirring for 45 minutes. Theresulting solution was added to 50 ml of tetrahydrofuran havingdissolved therein 12 ml (10 mmol) of dimethyldichlorosilane, and stirredat 25° C. for 30 minutes. After the stirring, 100 ml of heptane wasadded and tetrahydrofuran was distilled off. The heptane layer wasremoved and washed with hexane, followed by drying under vacuum. Theproduct was dissolved in 30 ml of dichloromethane, to which was added 20ml of a dichloromethane solution of 2.99 g (19.0 mmol) ofN,N-dimethylaniline hydrochloride. The solution was stirred for 30minutes and lithium chloride which precipitated was removed and driedunder vacuum to yield 1.6 g of dimethylanilinium4-dimethylchlorosilyl-2,3,5,6-tetrafluorophenyltris(pentafluorophenyl)borate.Its chemical structure was confirmed by NMR data measured (a part ofwhich is shown below).

¹ H-NMR (CD₂ Cl₂): δ0.77(6H), 3.23(6H), 7.50(6H), 7.57(3H), 11.5(1H);

¹⁹ F-NMR (CD₂ Cl₂): δ-128.6, -129.1, -130.0, -159.8, -163.6.

EXAMPLE 3 Production of Dimethylanilinium4-(8-(dimethylchlorosilyl)-octyldichlorosilyl-2,3,5,6-tetrafluorophenyl-tris(pentafluorophenyl)borateIonic Compound!

The same procedures as in Example 2 were repeated except that1,8-bis(dimethylchlorosilyl)octane was used in place ofdimethyldichlorosilane to yield 2.3 g of dimethylanilinium4-(8-(dimethylchlorosilyl)-octyldichlorosilyl)-2,3,5,6-tetrafluorophenyltris(pentafluorophenyl)borate.

COMPARATIVE EXAMPLE 1 Production of Dimethylanilinium4-dimethylchlorosilylphenyl-tris(pentafluorophenyl)borate IonicCompound!

The same procedures as in Example 2 were repeated except that1,4-dibromobenzene was used in place of 1,2,4,5-tetrafluorobenzene toyield 0.8 g of the target compound, dimethylanilinium4-dimethylchlorosilylphenyl-tris(pentafluorophenyl)borate.

EXAMPLE 4 Preparation of Components for Olefin Polymerization Catalystfrom the Compound of Example 1

To 30 ml of dichloromethane was added 0.5 g of silica dried at 150° C.and at 0.5 mmHg for 4 hours, with adding 6 ml of a dichloromethanesolution containing 56 μmol/ml of the ionic compound having a carrierbondable functional group obtained in Example 1 while stirring, and theresulting solution was refluxed for 2 hours. This was washed three timeswith 20 ml of dichloromethane at 40° C. and dried under vacuum.

The olefin polymerization catalyst component thus obtained was measuredfor its boron content by Induction Combined High Frequency Plasma (ICP)spectrophotometry. As a result, it was confirmed that the 0.25 mmol ofthe ionic compound of Example 1 was carried per g of the catalystcomponent. After the carrying, the amount of hydroxyl groups on thesurface of silica was determined by measuring the amount of ethane whichis formed as a result of the reaction between the hydroxyl groups on thesurface of silica and triethylaluminum. As a result, the hydroxyl groupsof the silica moiety was confirmed to be decreased by about 0.25 mmol/g.From this result, it is understood that substantially all the ioniccompounds carried on silica reacted with the hydroxyl groups on thesurface of silica. Further, formation of hydrogen chloride upon thereaction between the ionic compounds and silica by contacting thegaseous dichloromethane used in the reaction solvent with water,neutralizing with sodium carbonate and titrating with an aqueous silvernitrate solution using potassium chromate as an indicator.

The olefin polymerization catalyst component thus obtained was washedthree times with boiling dichloromethane. There was observed almost nochange in the amount of the ionic compound carried, which confirmed thatthe ionic compound and the carrier bonded to each other with sufficientstrength.

EXAMPLE 5 Preparation of Components for Olefin Polymerization Catalystfrom the Compound of Example 2

An olefin polymerization catalyst component was prepared in the samemanner as in Example 4 except that the compound of Example 2 was used asthe ionic compound having a carrier bondable functional group. Theamount of the ionic compound carried was 0.27 (mmol of ionic compound/gof catalyst component).

EXAMPLE 6 Preparation of Components for Olefin Polymerization Catalystfrom the Compound of Example 3

An olefin polymerization catalyst component was prepared in the samemanner as in Example 4 except that the compound of Example 3 was used asthe ionic compound having a carrier bondable functional group. Theamount of the ionic compound carried was 0.23 (mmol of ionic compound/gof catalyst component).

COMPARATIVE EXAMPLE 2 Preparation of Components for OlefinPolymerization Catalyst from the Compound of Comparative Example 1

An olefin polymerization catalyst component was prepared in the samemanner as in Example 4 except that the compound of Comparative Example 1was used as the ionic compound having a carrier bondable functionalgroup. The amount of the ionic compound carried was 0.17 (mmol of ioniccompound/g of catalyst component).

COMPARATIVE EXAMPLE 3 Preparation of Comparative Olefin PolymerizationCatalyst Component

A comparative olefin polymerization catalyst component was prepared inthe same manner as in Example 4 except that N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate was used in place of the ioniccompound having a carrier bondable functional group. The amount of theionic compound carried was less than 0.005 (mmol of ionic compound/g ofcatalyst component).

EXAMPLE 7 Preparation of an Olefin Polymerization Catalyst from theCatalyst Component of Example 4 and Olefin Polymerization

Preparation of Catalyst!

4 ml of a solution containing 0.5 mmol ofrac-ethylene-bisindenylzirconium dichloride (hereafter, abbreviated as"EBIZ")/liter of toluene was contacted with 0.2 ml of a solution of 0.5mol of triisobutylaluminum/liter of toluene, to which was added 30 mg ofthe olefin polymerization catalyst component of Example 4. Afterstirring the solution for 2 minutes, toluene was removed and 5.0 ml ofhexane was added to form a hexane slurry.

Polymerization of Propylene!

In a 1.5 liter autoclave were charged 6 ml of a hexane solution of 0.5mol of triisobutylaluminum/liter of hexane and 8 mol of propylene. Afterelevating the temperature to 50° C., the above-described slurry typeolefin polymerization catalyst was added and polymerization wascontinued for 60 minutes. The polymerization activity was 85,000 g/g ofcomplex/h, and 2,000 g/g of catalyst/h. Table 1 shows the resultsobtained. The bulk density of the resulting polymer was as high as 0.40g/ml, showing no attachment to the wall of the reactor.

EXAMPLE 8 Preparation of an Olefin Polymerization Catalyst from theCatalyst Component of Example 5 and Olefin Polymerization

Preparation of Catalyst!

30 mg of the olefin polymerization catalyst component of Example 5 wascontacted with 1.0 ml of a solution containing 0.5 mol oftriisobutylaluminum/liter of toluene, to which was added 4.0 ml of asolution containing 0.5 mol of EBIZ/liter of toluene. After stirring thesolution for 3 minutes, toluene was removed and 5.0 ml of hexane wasadded to form a hexane slurry.

Polymerization of Propylene!

The procedures of Example 7 were repeated except that theabove-described olefin polymerization catalyst was used. As a result,granular polymer was obtained. Table 1 shows the results.

Copolymerization of Propylene with Ethylene!

In a 5 liter autoclave were charged 6 ml of a hexane solution of 0.5 molof triisobutylaluminum/liter of hexane and 8 mol of propylene. Afterelevating the temperature to 50° C., the pressure was raised so that thepartial pressure of ethylene reached 1 kg/cm², and the above-describedolefin polymerization catalyst was added and polymerization wascontinued for 30 minutes. Table 2 shows the results. The polymerizationactivity was 130,000 g/g of complex/h/atm, and 10,000 g/g of catalyst/h.The resulting polymer was granular and had a bulk density as high as0.35 g/ml, showing no attachment to the wall of the reactor.

Polymerization of Ethylene!

In a 1.5 liter autoclave were charged 8 ml of a toluene solution of 0.5mol of triisobutylaluminum/liter of toluene, 100 mg of the olefinpolymerization catalyst, and 700 ml of isobutane. After elevating thetemperature to 70° C., the pressure was raised so that the partialpressure of ethylene reached 10 kg/cm², and polymerization was continuedfor 30 minutes. The polymerization activity was 150,000 g/g ofcomplex/h/atm, and 1,000 g/g of catalyst/h/atm. Table 3 shows theresults. The resulting polymer had a bulk density as high as 0.35 g/ml,showing no attachment to the wall of the reactor.

EXAMPLE 9 Preparation of an Olefin Polymerization Catalyst from theCatalyst Component of Example 4 and Olefin Polymerization

Preparation of Catalyst!

An olefin polymerization catalyst was prepared in the same manner as inExample 8 except that removal of the supernatant, washing with toluene,and slurry formation with hexane were not carried out.

Polymerization of Propylene!

In a 1.5 liter autoclave were charged 1.0 ml of a hexane solution of 0.1mol of n-butyllithium/liter of hexane and 8 mol of propylene. Afterelevating the temperature to 50° C., the above-described olefinpolymerization catalyst was added and polymerization was continued for60 minutes. Table 1 shows the results. The polymer was granular andshowed no attachment to the wall of the reactor.

Copolymerization of Propylene with Ethylene!

In a 1.5 liter autoclave were charged 1.0 ml of a hexane solution of 0.1mol of n-butyllithium/liter of hexane and 8 mol of propylene. Afterelevating the temperature to 50° C., the pressure was raised so that thepartial pressure of ethylene reached 1.0 kg/cm², and the above-describedolefin polymerization catalyst was added and polymerization wascontinued for 30 minutes. Table 2 shows the results. The resultingpolymer was granular and showed no attachment to the wall of thereactor.

Polymerization of Ethylene!

In a 1.5 liter autoclave were charged 1.0 ml of a hexane solution of 0.1mol of n-butyllithium/liter of hexane and 700 ml of isobutane. Afterelevating the temperature to 70° C., the pressure was raised so that thepartial pressure of ethylene reached 10.0 kg/cm², and polymerization wascontinued for 60 minutes. Table 3 shows the results. The resultingpolymer was granular and showed no attachment to the wall of thereactor.

EXAMPLE 10 Preparation of an Olefin Polymerization Catalyst from theCatalyst Component of Example 5 and Olefin Polymerization

Preparation of Catalyst!

An olefin polymerization catalyst was prepared in the same manner as inExample 8 except that the olefin polymerization catalyst component ofExample 5 was used.

Polymerization of Propylene!

The propylene polymerization procedures of Example 8 were repeatedexcept that the above-described olefin polymerization catalyst was usedto yield a granular polymer. Table 1 shows the results.

Copolymerization of Propylene and Ethylene!

The procedures of copolymerization of propylene and ethylene describedin Example 8 were repeated except that the above-described olefinpolymerization catalyst was used to yield a granular polymer. Table 2shows the results.

Polymerization of Ethylene!

The ethylene polymerization procedures of Example 8 were repeated exceptthat the above-described olefin polymerization catalyst was used toyield a granular polymer. Table 3 shows the results.

EXAMPLE 11 Preparation of an Olefin Polymerization Catalyst from theCatalyst Component of Example 6 and Olefin Polymerization

Preparation of Catalyst!

An olefin polymerization catalyst was prepared in the same manner as inExample 8 except that the olefin polymerization catalyst component ofExample 6 was used.

Polymerization of Propylene!

The propylene polymerization procedures of Example 8 were repeatedexcept that the above-described olefin polymerization catalyst was usedto yield a granular polymer. Table 1 shows the results.

Copolymerization of Propylene and Ethylene!

The procedures of copolymerization of propylene and ethylene describedin Example 8 were repeated except that the above-described olefinpolymerization catalyst was used to yield a granular polymer. Table 2shows the results.

Polymerization of Ethylene!

The ethylene polymerization procedures of Example 8 were repeated exceptthat the above-described olefin polymerization catalyst was used toyield a granular polymer. Table 3 shows the results.

EXAMPLE 12 Preparation of an Olefin Polymerization Catalyst from theCatalyst Component of Example 4 and Olefin Polymerization

Preparation of Catalyst!

An olefin polymerization catalyst was prepared in the same manner as inExample 8 except thatrac-isopropylidene(3-t-butylcyclopentadienyl){1-(3-t-butylindenyl)}zirconiumdichloride (hereafter, abbreviated as "CTITZ") was used instead of EBIZ.

Polymerization of Propylene!

The propylene polymerization procedures of Example 8 were repeatedexcept that the above-described olefin polymerization catalyst was usedto yield a granular polymer. Table 1 shows the results.

Copolymerization of Propylene and Ethylene!

The procedures of copolymerization of propylene and ethylene describedin Example 8 were repeated except that the above-described olefinpolymerization catalyst was used to yield a granular polymer. Table 2shows the results.

Polymerization of Ethylene!

The ethylene polymerization procedures of Example 8 were repeated exceptthat the above-described olefin polymerization catalyst was used toyield a granular polymer. Table 3 shows the results.

EXAMPLE 13 Preparation of an Olefin Polymerization Catalyst from theCatalyst Component of Example 4 and Olefin Polymerization

Preparation of Catalyst!

An olefin polymerization catalyst was prepared in the same manner as inExample 8 except thatrac-dimethylsilylenebis{1-(2-methyl-4-benzoindenyl)}zirconium dichloride(hereafter, abbreviated as "2MBIZ") was used instead of EBIZ.

Polymerization of Propylene!

The propylene polymerization procedures of Example 8 were repeatedexcept that the above-described olefin polymerization catalyst was usedto yield a granular polymer. Table 1 shows the results.

Copolymerization of Propylene and Ethylene!

The procedures of copolymerization of propylene and ethylene describedin Example 8 were repeated except that the above-described olefinpolymerization catalyst was used to yield a granular polymer. Table 2shows the results.

Polymerization of Ethylene!

The ethylene polymerization procedures of Example 8 were repeated exceptthat the above-described olefin polymerization catalyst was used toyield a granular polymer. Table 3 shows the results.

EXAMPLE 14 Preparation of an Olefin Polymerization Catalyst from theCatalyst Component of Example 4 and Olefin Polymerization

Preparation of Catalyst!

An olefin polymerization catalyst was prepared in the same manner as inExample 8 except thatrac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride (hereafter, abbreviated as "2MPIZ") was used instead of EBIZ.

Polymerization of Propylene!

The propylene polymerization procedures of Example 8 were repeatedexcept that the above-described olefin polymerization catalyst was usedto yield a granular polymer. Table 1 shows the results.

Copolymerization of Propylene and Ethylene!

The procedures of copolymerization of propylene and ethylene describedin Example 8 were repeated except that the above-described olefinpolymerization catalyst was used to yield a granular polymer. Table 2shows the results.

Polymerization of Ethylene!

The ethylene polymerization procedures of Example 8 were repeated exceptthat the above-described olefin polymerization catalyst was used toyield a granular polymer. Table 3 shows the results.

EXAMPLE 15 Preparation of an Olefin Polymerization Catalyst from theCatalyst Component of Example 4 and Olefin Polymerization

Preparation of Catalyst!

An olefin polymerization catalyst was prepared in the same manner as inExample 8 except thatrac-dimethylsilylenebis{1-(2-methyl-4-naphthylindenyl) }zirconiumdichloride (hereafter, abbreviated as "2MNIZ") was used instead of EBIZ.

Polymerization of Propylene!

The propylene polymerization procedures of Example 8 were repeatedexcept that the above-described olefin polymerization catalyst was usedto yield a granular polymer. Table 1 shows the results.

Copolymerization of Propylene and Ethylene!

The procedures of copolymerization of propylene and ethylene describedin Example 8 were repeated except that the above-described olefinpolymerization catalyst was used to yield a granular polymer. Table 2shows the results.

Polymerization of Ethylene!

The ethylene polymerization procedures of Example 8 were repeated exceptthat the above-described olefin polymerization catalyst was used toyield a granular polymer. Table 3 shows the results.

COMPARATIVE EXAMPLE 4 Preparation of an Olefin Polymerization Catalystfrom the Catalyst Component of Comparative Example 3 and OlefinPolymerization

Preparation of Catalyst!

An olefin polymerization catalyst was prepared in the same manner as inExample 8 except that the olefin polymerization catalyst component ofComparative Example 3 was used.

Polymerization of Propylene!

The propylene polymerization procedures of Example 8 were repeatedexcept that the above-described olefin polymerization catalyst was used.Table 1 shows the results. Almost no polymerization activity wasobserved.

Copolymerization of Propylene and Ethylene!

The procedures of copolymerization of propylene and ethylene describedin Example 8 were repeated except that the above-described olefinpolymerization catalyst was used. Table 2 shows the results. Almost nopolymerization activity was observed.

Polymerization of Ethylene!

The ethylene polymerization procedures of Example 8 were repeated exceptthat the above-described olefin polymerization catalyst was used. Table3 shows the results. Almost no polymerization activity was observed.

COMPARATIVE EXAMPLE 5 Preparation of Comparative Olefin PolymerizationCatalyst and Olefin Polymerization

Preparation of Catalyst!

4 ml of a solution of 0.5 mmol of EBIZ/liter of toluene was contactedwith 0.2 ml of a solution of 0.5 mol of triisobutylaluminum/liter oftoluene, to which was added 2 ml of a solution of 1 mmol ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate/liter oftoluene. After stirring for 2 minutes, 30 mol of toluene and 0.5 g ofsilica (dried at 450° C. for 4 hours) were added. After stirring thesolution for 5 minutes, toluene was removed and the residue was washedwith hexane and converted into a hexane slurry.

Polymerization of Propylene!

In a 1.5 liter autoclave were charged 6 ml of a hexane solution of 0.5mol of triisobutylaluminum/liter of hexane and 8 mol of propylene. Afterelevating the temperature to 50° C., the above-described olefinpolymerization catalyst was added and polymerization was continued for30 minutes. The polymerization activity was 7,400 g/g of complex/h, and130 g/g of catalyst/h. Table 1 shows the results obtained. The resultingpolymer had a bulk density as high as 0.12 g/ml and was fine powdershowing attachment to the wall of the reactor to some extent.

Copolymerization of Propylene and Ethylene!

The procedures of copolymerization of propylene and ethylene describedin Example 8 were repeated except that the above-described olefinpolymerization catalyst was used. Table 2 shows the results. Theresulting polymer was fine powder showing attachment to the wall of thereactor to some extent.

Polymerization of Ethylene!

The ethylene polymerization procedures of Example 8 were repeated exceptthat the above-described olefin polymerization catalyst was used. Table3 shows the results.

COMPARATIVE EXAMPLE 6 Preparation of an Olefin Polymerization Catalystfrom the Catalyst Component of Comparative Example 2 and OlefinPolymerization

Preparation of Catalyst!

An olefin polymerization catalyst was prepared in the same manner as inExample 8 except that the olefin polymerization catalyst component ofComparative Example 2 was used.

Polymerization of Propylene!

The propylene polymerization procedures of Example 8 were repeatedexcept that the above-described olefin polymerization catalyst was used.A granular polymer was obtained. Table 1 shows the results.

Copolymerization of Propylene and Ethylene!

The procedures of copolymerization of propylene and ethylene describedin Example 8 were repeated except that the above-described olefinpolymerization catalyst was used. A granular polymer was obtained. Table2 shows the results.

Polymerization of Ethylene!

The ethylene polymerization procedures of Example 8 were repeated exceptthat the above-described olefin polymerization catalyst was used. Table3 shows the results.

                  TABLE 1    ______________________________________    Polymerization of Propylene    Activity of Polymerization                          Density  Attachment    Example gPP/complex/h                       gPP/Catalyst/h                                  g/ml   of Polymer    ______________________________________     7      85,000     2,000      0.40   No     8      30,000       600      0.41   No     9      66,000     1,700      0.40   No    10      100,000    7,000      0.43   No    11      62,000     3,300      0.39   No    12      55,000     3,000      0.40   No    13      31,000     1,700      0.40   No    14      20,000     1,500      0.35   No    15      40,000     2,000      0.40   No    C. Ex. 4               0          0       --     --    C. Ex. 5             7,400       130      0.12   Yes    C. Ex. 6             5,000       300      0.37   No    ______________________________________

                  TABLE 2    ______________________________________    Copolymerization of Propylene and Ethylene    Activity of Polymerization           gPP/mmol                Density                                         Attachment    Example           Complex/h   gPP/g Catalyst/h                                   g/ml  of Polymer    ______________________________________     8     130,000     10,000      0.35  No     9     260,000     11,000      0.35  No    10     320,000     29,000      0.35  No    11     160,000     10,000      0.37  No    12     380,000      6,300      0.32  No    13     230,000     13,000      0.33  No    14     310,000     21,000      0.30  No    15     100,000      7,000      0.39  No    C. Ex. 4               0          0        --    --    C. Ex. 5            30,000      3,000      0.13  Yes    C. Ex. 6            20,000      2,000      0.35  No    ______________________________________

                  TABLE 3    ______________________________________    Polymerization of Ethylene    Activity of Polymerization    Ex-   gPE/mmol                 Density                                         Attachment    ample Complex/h/atm                     gPE/g Catalyst/h/atm                                   g/ml  of Polymer    ______________________________________     8    150,000    1,000         0.35  No     9    100,000    2,000         0.32  No    10    70,000     1,200         0.32  No    11    75,000     1,500         0.35  No    12    70,000       600         0.31  No    13    70,000     1,000         0.31  No    14    11,000     1,300         0.34  No    15    60,000       550         0.35  No    C. Ex. 4             0          0          --    --    C. Ex. 5          80,000       200         0.15  Yes    C. Ex. 6           8,000       140         0.33  No    ______________________________________

INDUSTRIAL APPLICABILITY

The ionic compound of this invention, which is used in combination witha carrier, an organometal compound and a Group 4, 5 or 6 transient metalcompound, is useful as a catalyst component for olefin polymerization bya slurry process, gas phase process or the like. Using the ioniccompound of this invention, catalysts having excellent bonding abilitywith the carrier can be obtained and it is possible therewith to producepolyolefins having improved powder characteristics and showing noattachment to the inner wall of a reactor.

The catalyst of this invention is useful for producing a wide variety ofpolymers from monomers such as ethylene, propylene, 1-butene,3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene,cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene,tetracyclododecene, and further styrene, vinylcyclohexane,vinylcyclohexene, divinylbenzene, dienes, etc.

We claim:
 1. Ionic compounds represented by general formula (I) below:

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R4-L).sub.n !.sup.-  D!.sup.+                                                 (I)

wherein, M is an element belonging to Group 13; R¹, R² and R³, which maybe the same or different, each represent a C₁ -C₂₀ hydrocarbyl group, asubstituted hydrocarbyl group, an alkoxide group, or a halogen atom; R⁴represents a C₁ -C₂₀ alkylene group, a substituted alkylene group, asubstituted phenylene group, a silanylene group, a substitutedsilanylene group, a silalkylene group, a substituted silalkylene group,an oxasilanylene group, a substituted oxasilanylene group, or anoxasilalkylene group, with k, l and m each being 0 or an integer of 1 to3, and n being an integer of 1 to 4 such that k+l+m+n=4; L is a grouprepresented by general formula (II) or (III) below and is chemicallybonded to R⁴ :

    SiR.sup.5 R.sup.6 R.sup.7                                  (II)

    R.sup.8 R.sup.9 R.sup.10 SiYSiR.sup.11 R.sup.12            (III)

wherein R⁵ to R¹², which may be the same or different, each represent aC₁ -C₂₀ hydrocarbyl group, a substituted hydrocarbyl group, an alkoxidegroup, or a halogen atom, with at least one of R⁵, R⁶ and R⁷ and atleast one of R⁸, R⁹ and R¹⁰ being a halogen atom; Y is --O--, a C₁ -C₂₀alkylene group, a substituted alkylene group, a phenylene group, asubstituted phenylene group, or a group represented by formula:

    --(Z.sup.1 SiZ.sup.2 Z.sup.3 Z.sup.4).sub.r --

wherein Z¹ and Z⁴, which may be the same or different, each represent analkylene group, a substituted alkylene group, a phenylene group, asubstituted phenylene group, --O--, an oxyalkylene group, a substitutedoxyalkylene group, an oxyphenylene group, or a substituted oxyphenylenegroup; Z² and Z³, which may be the same or different, each represent ahydrogen atom, an alkyl group, a substituted alkyl group, a phenylgroup, or a substituted phenyl group; r is an integer of at least 1;when n is 2 or more, each R⁴ -L may be the same or different; D is amonovalent cation selected from the group consisting of carbonium,anilinium, ammonium, ferrocenium, phosphonium, sodium, potassium, orlithium.
 2. The ionic compound as claimed in claim 1, wherein n is
 1. 3.The ionic compound as claimed in claim 1, wherein M is boron.
 4. Theionic compound as claimed in claim 1, wherein R¹, R² and R³ are each apentafluorophenyl group.
 5. The ionic compound as claimed in claim 1,wherein L is a halogenated silyl group, a halogenated substituted silylgroup, a halogenated silalkyl group, a halogenated substituted silalkylgroup, a halogenated oxasilyl group, a halogenated substituted oxasilylgroup, or a halogenated oxasilalkyl group.
 6. The ionic compound asclaimed in claim 1, wherein R⁴ is a substituted phenylene group.
 7. Theionic compound as claimed in claim 6, wherein R⁴ is a2,3,5,6-tetrafluorophenylene group.
 8. The ionic compound as claimed inclaim 1, wherein L is a trichlorosilyl group, a methyldichlorosilylgroup, or a dimethylchlorosilyl group.
 9. The ionic compound as claimedin claim 1, wherein D is an anilinium ion.
 10. A method of producingionic compounds represented by general formula (I)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -L).sub.n !.sup.-  D!.sup.+                                         (I)

wherein M, R¹, R², R³, R⁴, L, D, k, l, m, and n in the formula have thesame meanings as in claim 1, comprising the steps of: reactingcomponents represented by (1) to (4) below: (1) a compound representedby general formula (IV):

    X.sup.1 -R.sup.4 -X.sup.2                                  (IV)

wherein X¹ and X² independently represent a hydrogen atom or a bromineatom, and R⁴ has the same meaning as in claim 1; (2) a compoundrepresented by general formula (V):

    MR.sup.1 R.sup.2 R.sup.3                                   (V)

wherein M is an element belonging to Group 13; and R¹, R² and R³, whichmay be the same or different, each represent a C₁ -C₂₀ hydrocarbylgroup, a substituted hydrocarbyl group, an alkoxide group or a halogenatom; (3) a compound represented by general formula (VI) or (VII):

    SiR.sup.5 R.sup.6 R.sup.7 R.sup.13                         (VI)

    R.sup.8 R.sup.9 R.sup.10 SiYSiR.sup.11 R.sup.12 R.sup.14   (VII)

wherein R⁵ to R¹⁴, which may be the same or different, each represent aC₁ -C₂₀ hydrocarbyl group, a substituted hydrocarbyl group, an alkoxidegroup, or a halogen atom; and (4) a halide of a monovalent cation.
 11. Amethod of producing ionic compounds represented by general formula (I)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -L).sub.n !.sup.-  D!.sup.+                                         (I)

wherein M, R¹, R², R³, R⁴, L, D, k, l, m, and n in the formula have thesame meanings as in claim 1, comprising the steps of: (a) substitutingbromine or hydrogen of a compound represented by general formula (IV)

    X.sup.1 -R.sup.4 -X.sup.2                                  (IV)

wherein X¹ and X² independently represent a hydrogen atom or a bromineatom, and R⁴ represents a C₁ -C₂₀ alkylene group, a substituted alkylenegroup, a substituted phenylene group, a silanylene group, a substitutedsilanylene group, a silalkylene group, a substituted silalkylene group,an oxasilanylene group, a substituted oxasilanylene group, or anoxasilalkylene group, with lithium of an organic lithium to obtain alithium substituted compound; (b) reacting the lithium substitutedcompound with a Group 13 element-containing compound represented bygeneral formula (V)

    MR.sup.1 R.sup.2 R.sup.3                                   (V)

wherein R¹, R² and R³, which may be the same or different, eachrepresent a C₁ -C₂₀ hydrocarbyl group, a substituted hydrocarbyl group,an alkoxide group or a halogen atom, to obtain a lithium compoundrepresented by formula (VIII)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -A).sub.n !.sup.-  Li!.sup.+                                        (VIII)

wherein A is hydrogen or bromine chemically bonded to R⁴ ; (c)lithionating the compound of general formula (VIII) with an organiclithium and then reacting with a silicon compound represented by generalformula (VI) or (VII) below

    SiR.sup.5 R.sup.6 R.sup.7 R.sup.13                         (VI)

    R.sup.8 R.sup.9 R.sup.10 SiYSiR.sup.11 R.sup.12 R.sup.14   (VII)

wherein R⁵ to R¹⁴, which may be the same or different, each represent aC₁ -C₂₀ hydrocarbyl group, a substituted hydrocarbyl group, an alkoxidegroup, or a halogen atom, to obtain a compound represented by generalformula (IX)

     M(R.sup.1).sub.k (R.sup.2).sub.l (R.sup.3).sub.m (R.sup.4 -L).sub.n !.sup.-  Li!.sup.+                                        (IX); and

(d) reacting the compound of general formula (IX) with a halide of amonovalent cation.
 12. The method of producing the ionic compounds asdescribed! claimed in claim 10 or 11, wherein the compound of generalformula (IV) is a compound represented by general formula (IVa) ##STR4##wherein X¹ and X² independently represent a hydrogen atom or a bromineatom.
 13. A catalyst component for olefin polymerization comprising theionic compound as claimed in claim 1 chemically bonded to a carrier. 14.The catalyst component as claimed in claim 13, wherein the carrier is asolid having a functional group represented by general formula (X)

    --OR                                                       (X)

wherein R is a hydrogen atom, a C₁ -C₂₀ alkyl group, alkali metal oramine.
 15. The catalyst component as claimed in claim 14, wherein thecarrier is a solid having a hydroxyl group.
 16. The catalyst componentas claimed in claim 13, wherein the carrier is silica, alumina ormixtures thereof.
 17. A catalyst for olefin polymerization comprisingthe following as essential components:(a) the catalyst component forolefin polymerization as claimed in claim 13, (b) an organometalliccompound, and (c) a Group 4, 5 or 6 transtion metal compound.
 18. Thecatalyst as claimed in claim 17, wherein the Group 4, 5 or 6 transitionmetal compound is a metallocene.